US3580960A - Dehydrogenation catalyst - Google Patents

Dehydrogenation catalyst Download PDF

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Publication number
US3580960A
US3580960A US834557A US3580960DA US3580960A US 3580960 A US3580960 A US 3580960A US 834557 A US834557 A US 834557A US 3580960D A US3580960D A US 3580960DA US 3580960 A US3580960 A US 3580960A
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United States
Prior art keywords
dehydrogenation
catalyst
process according
platinum group
range
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Expired - Lifetime
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US834557A
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English (en)
Inventor
Ian Montgomery Keen
Peter James Craig
Christopher Patrick Cadman
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BP PLC
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BP PLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica

Definitions

  • This invention relates to dehydrogenation catalysts and to dehydrogenation processes in which they are used.
  • felspar may be used in the place of the molecular sieve as a support for the platinum group metal.
  • the catalysts of the present invention besides being useful for the dehydrogenation of n-alkanes to n-alkenes are also suitable for the dehydrocyclization of n-alkanes, for example the preparation of benzene from n-hexane.
  • a process for the production of a catalyst suitable for the dehydrogenation of n-alkanes which process comprises exchanging a platinum group metal onto a felspar.
  • platinum group metal we mean the metals palladium, platinum, osmium, iridium, ruthenium and rhodium.
  • a felspar is defined as an aluminosilicate which has an empirical formula approximating to Na K Ca AlSi O
  • the final platinum group metal content of the catalyst is in the range 0.01 to 5% by weight of the total weight of the catalyst, preferably 0.1-1%
  • the platinum group metal is platinum or palladium.
  • the preferred felspar is albite, which has the empirical formula NaAlSi O It is a naturally occurring mineral, but can also be synthesised.
  • the final alkali or alkaline earth metal ion content of the catalyst is in the range 0.3 to 3.5% by weight of the total weight of the catalyst preferably 0.6 to 1.5%.
  • Alkali metal ions are more satisfactory than alkaline earth metal ions and the preferred ion is sodium.
  • Suitable normal alkanes which may be dehydrogenated include those containing from 3 to 30, preferably 6 to 18 carbon atoms per molecule.
  • Dehydrogenation is suitably effected in the range 300- 650 C.
  • Pressure should be between 10 mm. mercury and 1000 p.s.i.g. and preferably between 0 and 50 p.s.i.g.
  • the alkane may be passed over the catalyst at an LHSV in the range 0.1 to 40 vol./vol.
  • the alkane LHSV is in the range 2-15 vo1./ vol.
  • dehydrogenation is preferably effected in the presence of added hydrogen.
  • the molar ratio of added hydrogen to the alkane feedstock is in the range 0.130, preferably between 2 and 10.
  • a catalystof greater Group VIII metal concentrations may be prepared by further exchanges, e.g.,
  • Catalysts may also be prepared by direct impregnation with platinum group metal salts. This is not the preferred technique, however.
  • the sodium ions shown in the first exchange reaction are those normally presented on the felspar. Any deliberate incorporation of alkali or alkaline earth metal ions takes place after reduction and corresponds to the second exchange reaction:
  • the reduction takes place by contacting the exchanged felspar with hydrogen at elevated temperature.
  • EXAMPLE 1 (A) Preparation of albite Albite was prepared using essentially the method of Barrer & White (J. Chem. Soc., 1952, 1561 and ibid., 1951, 1267). The preparation was in two parts.
  • a catalyst designated Pt.Na+ albite was prepared as follows. 30 g. of albite (30-60 mesh BSS) was contacted with a stirred solution of Pt(NH Cl (0.264 g.) in water (50 ml.) for 4 hours at 80 C. The product was filtered and washed with distilled Water until the washings were chloride free and then dried, first on a Buchner pump and then in nitrogen GHSV 1000, for 3 hours at 120 C. and then at temperatures raised by 50 C. per hour to 450 C. Hydrogen was then passed at GHSV 1000 for 1 hour. After cooling, the product (Pt.H+ albite) was carefully moistened and exchanged with 100 ml. of 0.1 N NaHCO at 80 C. for 4 hours and then filtered, washed several times with distilled water dried at the pump and then in nitrogen as above. The resulting catalyst Pt.Na+ albite was found to contain 0.6% wt.
  • EXAMPLE 2 ml. of Pt.Na+ albite prepared as in Example 1 was charged to a stainless steel reactor which was then heated to a temperature of 450 C. After purging with nitrogen n-undecane was passed at LHSV 4 together with 2 moles of hydrogen per mole of undecane at a pressure of 25 p.s.i.g. Analysis of the product showed that 13% of the n-undecane was converted with 80% selectivity to nundecenes.
  • Example 3 The procedure of Example 1 was repeated except that n-hexane was passed at LHSV of 1.2 together with 2.5 moles of hydrogen per mole of n-hexane. The reaction 4 temperature was 550 C. A 73% conversion of the nhexane was effected to yield a product containing 2% hexenes, 83% benzene, 1% ends and 14% others.
  • a process for the production of a catalyst suitable for the dehydrogenation of n-alkanes which process comprises exchanging a platinum group metal onto a felspar.
  • a process for the dehydrogenation of a normal alkane which process comprises contacting the alkane at elevated temperature with a catalyst prepared by exchanging a platinum group metal onto a felspar.
  • a process according to claim 11 wherein the alkane which is dehydrogenated contains from 3 to 30 carbon atoms per molecule.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US834557A 1968-07-29 1969-06-18 Dehydrogenation catalyst Expired - Lifetime US3580960A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB35992/68A GB1211158A (en) 1968-07-29 1968-07-29 Dehydrogenation catalyst

Publications (1)

Publication Number Publication Date
US3580960A true US3580960A (en) 1971-05-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
US834557A Expired - Lifetime US3580960A (en) 1968-07-29 1969-06-18 Dehydrogenation catalyst

Country Status (6)

Country Link
US (1) US3580960A (fr)
BE (1) BE736729A (fr)
DE (1) DE1937581A1 (fr)
FR (1) FR2013889A1 (fr)
GB (1) GB1211158A (fr)
NL (1) NL6911442A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686341A (en) * 1970-08-31 1972-08-22 Paul E Eberly Jr Process for aromatization of olefin hydrocarbons

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686341A (en) * 1970-08-31 1972-08-22 Paul E Eberly Jr Process for aromatization of olefin hydrocarbons

Also Published As

Publication number Publication date
BE736729A (fr) 1970-01-29
GB1211158A (en) 1970-11-04
NL6911442A (fr) 1970-02-02
DE1937581A1 (de) 1971-02-11
FR2013889A1 (fr) 1970-04-10

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